Beruflich Dokumente
Kultur Dokumente
The Marvin Sktech Software was used to evaluate Alliins protonation state at physiological pH (7.2).
The result of the simulation is shown in Fig. S6. The Infrared and Raman spectra presented in the paper are
for the most stable conformer, depicted in Fig. 1b and labeled here Alliin 1. In Fig.S7, we present the DFT
calculated vibrational spectra of both conformers together with the Allicin theoretical spectra. We also provide
the structural parameters of both Alliins conformers in Table S3, and complete vibrational assignments of
Alliins normal modes (not discussed in the paper) in Table S4.
Figure SF1. Marvin sketch computation of Alliins Microspecies distribution along 0 14 pH range.
Figure SF2. DFT-calculated Infrared (left) and Raman (right) spectra of both Alliin conformers and Allicin in
the wanumber range 1100-1800 cm-1.
Figure SF3. DFT-calculated Infrared (left) and Raman (right) spectra of Alliin in the 1800-3600 cm -1 range.
The infrared experimental spectrum of Alliin in the 1800-3900 cm -1 wavenumber range is shown at the top-left
of Fig. SF3. It shows a series of strongly shifted bands with large broadening, probably due to the lack of
homogeneity of the Alliin powder samples. Water effects (OH stretching) can contribute to the shape of the
experimental curve near 3600 cm -1. Experimental peaks at 2030, 2580, and 3080 cm -1 are assigned to the
theoretical normal modes M50, M59, and M60 (Fig. SF3, bottom-left). The Raman experimental spectrum, on
the other hand, exhibits much less broadening between 2700 and 3150 cm -1 (top-right), while the theoretical
curve is shifted up by about 200 cm-1. The main Raman peaks are assigned to the normal modes M55, M56,
M57, and M58.
Table ST1. Calculated structural parameters for the lowest energy Alliin conformers. Bond lengths and
angles are displayed in and degrees, respectively.
Atoms
C1H3
C1H2
C1C4
C4H5
C4C6
C6H7
C6H8
C6S15
S15O16
S15C9
C9H10
C9H11
C9C12
C12H13
C12C14
C12N17
N17H18
N17H19
N17H20
C14O21
C14O22
Bond lenght
Conformer 1
Conformer 2
1.0853
1.0833
1.3285
1.0862
1.4951
1.0911
1.0917
1.8308
1.5415
1.8261
1.0901
1.0910
1.5226
1.0913
1.5627
1.4979
1.0189
1.0322
1.0462
1.2377
1.2489
1.0851
1.0833
1.3284
1.0861
1.4940
1.0917
1.0927
1.8294
1.5367
1.8234
1.0937
1.0902
1.5226
1.0893
1.5652
1.4975
1.0204
1.0298
1.0380
1.2378
1.2469
Atoms
H2C1H3
H2C1C4
C1C4H5
H5C4C6
C4C6H8
H8C6S15
C6S15C9
O16S15C9
H11C9C12
C9C12H13
C13C12N17
N17C12C14
O22C14O21
Bond angle
Conformer 1
Conformer 2
117.48
121.24
120.45
116.64
112.88
106.16
101.57
104.54
111.30
107.36
107.48
108.31
129.96
117.48
121.19
120.47
116.61
112.30
105.63
97.34
103.42
108.91
111.21
108.40
108.15
103.31
Table ST2. Alliin infrared and Raman active normal modes in the wavenumber range 400-1800 cm -1. The assignments of Xiao et al. 18
are also shown. is given in cm-1 and the deviations cm-1 (%) of each theoretical normal mode with respect to experimental values
are provided as well.
Mode
Infrared
THE
Raman
Our
Xiao
Our
Xiao
324
Skel
M13
378
421
417
415
C9H10H11(38), N17H18H19H20(15)
Skel
M14
442
463
461
461
C1C4C6(74)
NH3
M15
524
522
503
500
C12C9N17(60), C9H10H11(10)
Skel
M16
540
544
543
544
Skel
Skel
M17
580
585
588
588
S15C6(42), C1C4C6(26)
COO-
M18
610
614
617w
619
620m
Skel
COO-
M19
678
702
691w
693
693vs
S15C9(63)
C-S
M20
758
746
744w
745
745vs
S15C6(25), C1H2H3(24)
COO-
M21
803
787
783m
790
790vs
C14O21O22(37)
CH2, COO-
M22
849
841
850w
840
837m
C14O21O22(40), C9H10H11(13)
CH2
M23
888
873
873
M24
901
931
919s
931
934m
C9C12C14N17(33)
CH2
964m
967m
C-C
M25
956
990
989m
972
992w
C-C, C-N
M26
962
1019
S15O16(63), C1H2H3(20)
M27
978
1040
Skel
M28
989
990
C1H2H3(96)
M29
1034
1055
1048w
1054
1051w
C1H2H3(92)
S=O, C-N
M30
1087
1085
1100
C9C12C14(52)
M31
1106
1119
1124
M32
1145
1146
1131m
1148
M33
1147
1157
1158
M34
1231
1195
1229w
1197
M35
1246
1215
1207
M36
1278
1272
1277
M37
1314
1294
1301s
1291
M38
1325
---
1297
M39
1346
1319
1317
M40
1385
1357
1342s
1361
M41
1412
1391
1405
M42
1427
1430
M43
1442
1398
1418vs
M44
1460
1453
M45
1494
1431
M46
1614
1519
1496vs
M47
1669
1593
1582s
1593
M48
1723
1638
1617s
C1H2H3(40), C6H7H8(41)
1138s
N17H18H19H20(69)
NH3+
C9C12(14), N17H18H19H20(48)
C9C12(14), C9H10H11(15)
C7H7H8
C9H10H11(37), N17H18H19H20(20)
CH2, CH
C1C4H3H5(88), C6H7H8(10)
C9H10H11(49)
N17H18H19H20(43)
CH2, CH
SC14O21O22(70), C9H10H11(10)
C1H2H3(89), C9H10H11(10)
C9H10H11(84)
COO-
C1H2H3(89), C9H10H11(10)
SN17H18H19H20(77)
1197s
1290vs
1336m
1404vs
1502w
AN17H18H19H20(87)
AN17H18H19H20(98)
1636vs
AC14O21O22(82), C1C4(16)
NH3+
NH3+
NH3+
M49
1725
1646
1643
C1C4(70), AC14O21O22(10)
The symbols: ,,,,,and stand for stretching, in-plane angular deformation, out-of-plane deformation, twisting, rocking,
wagging and bending modes in this respective order, subscripts A and S stand for symmetric and asymmetric respectively and the term
Skel is assign to a vibration mode which the PED is distributed throughout the whole molecular skeleton.
Table ST3. All calculated normal modes for the Alliin molecule. The wavenumber is given in cm-1, with respective Infrared and/or Raman
experimental counterparts vibrational assignments. The deviation of each theoretical normal mode in comparison with experiment (in cm-1), is
presented as well .
Mode
THE
M01
M02
M03
M04
M05
M06
M07
M08
M09
M10
M11
M12
M13
M14
M15
M16
M17
M18
M19
M20
M21
M22
M23
M24
M25
M26
M27
M28
M29
M30
M31
M32
M33
M34
M35
M36
M37
M38
M39
M40
M41
M42
M43
M44
M45
M46
M47
M48
M49
M50
M51
M52
M53
M54
M55
M56
M57
M58
M59
M60
50
66
80
89
120
161
252
262
303
321
340
359
378
441
523
540
580
610
678
757
802
849
888
900
956
962
978
989
1033
1087
1106
1145
1147
1231
1246
1278
1314
1325
1346
1385
1412
1427
1442
1460
1494
1614
1669
1723
1725
3013
3089
3105
3120
3160
3164
3169
3187
3258
3333
3549
Experimental
IR
Raman
416
460
503
542
588
619
693
744
790
840
873
930
972
989
1054
1100
1124
1147
1157
1196
1207
1277
1291
1297
1316
1361
1404
1429
1453
1593
--1643
421
462
521
544
584
613
701
746
786
841
872
930
989
1018
1039
1054
1084
1118
1146
1156
1194
1214
1272
1294
1318
1357
1390
1397
1430
1519
1592
1637
1645
IR (%)
Raman (%)
-43 (10.2)
-21 (4.5)
+2 (0.3)
-4 (0.7)
-4 (0.7)
-3 (0.4)
-23 (3.2)
+11 (1.4)
+16 (2.0)
+8 (0.9)
+16 (1.8)
-30 (3.2)
-33 (3.3)
-56 (5.5)
-61 (5.8)
-21 (1.9)
+3 (0.2)
-12 (1.0)
-1 (0)
-9 (0.7)
+37 (3.0)
32 (2.6)
+6 (0.4)
+20 (1.5)
+28 (2.1)
+28 (2.0)
+2 (1.5)
+45 (3.2)
+64 (4.4)
+95 (6.2)
+77 (4.8)
+86 (5.2)
+70 (4.8)
-38 (9.1)
-19 (4.1)
+20 (3.9)
-2 (0.3)
-8 (1.3)
-9 (1.4)
-15 (2.1)
+13 (1.7)
+12 (1.5)
+9 (1.0)
+15 (1.7)
-30 (3.2)
-16 (1.6)
-21 (1.9)
-13 (1.1)
-18 (1.6)
-2 (1.0)
-10 (0.8)
+35 (2.9)
+39 (3.2)
+1 (0)
+23 (1.7)
+28 (2.1)
+30 (2.2)
+24 (1.7)
+8 (0.5)
-2 (0.1)
+7 (0.4)
+76 (4.7)
--+82 (4.9)
The symbols: ,,,,,and stand for stretching, in-plane angular deformation, out-of-plane deformation, twisting, rocking, wagging and
bending modes in this respective order, subscripts A and S stand for symmetric and asymmetric respectively and the term Skel is assign to a
vibration mode which the PED is distributed throughout the whole molecular skeleton.